Synergistic herbicidal mixture

ABSTRACT

New and valuable herbicide comprising a composition of several active ingredients.

United States Patent Fischer 1 June 10, 1975 1 SYNERGISTIC HERBICIDAL MIXTURE [56] References Cited [75] Inventor: Adolf Fischer, Mutterstadt, UNITED STATES PATENTS Germany 3,027,248 3/1962 Koopman et a1. 71/105 Assigneez Badische Anilin S0da Fabrik 3,708,277 1/1973 Ze1dler et a1. 71/91 Aktiengesellschaft, OTHER PUBLICATIONS Ludwlgshafen/Rhme, Germany Fischer, Herbicidal Compositions, 1970 CA73, 22 Filed: Mar. 22, 1973 1195341,

De Floor, Control of Chrysanthemum Segetum etc., [21] APPl- 343,629 1971 CA77, No. 44194k, 1972 [30] Foreign Application Priority Data Primary ExaminerGlennon l-l. Hollrah Apr. 13, 1972 Germany 2217722 Attorney, Agent, or Firm-J0hnSt0m Keil, Thompson & Shurtleff [52] U.S. Cl. 71/91; 71/88; 71/90;

71/94; 71/97; 71/103; 71/105; 71/106; [57] ABSTRACT 71/111; 71/114; 71/115; 71/121; 71/124 New and valuable herbicide comprising a composition [51] Int. Cl Aolll 9/12 of several active ingredients [58] Field of Search 71/91, 105

4 Claims, No Drawings 1 SYNERGISTIC HERBICIDAL MIXTURE The present invention relates to a herbicide comprising a composition of several active ingredients.

lt is known that substituted phenyl ethers. carbamates, terephthalates, acid amides, benzoic acids, fluorenecarboxylic acids and benzothiadiazinones have a herbicidal action. However, this action is poor.

I have now found that a composition of a. a compound of the formula where R denotes lower alkyl ofa maximum of4 carbon atoms, or its salts, such as alkali metal, alkaline earth metal, ammonium, hydroxyalkylammonium, alkylammonium and hydrazine salts, e.g. salts with sodium, lithium, potassium, calcium, iron, methylammonium, trimethylammonium, ethylammonium, diethanolammonium, ethanolammonium, dimethylamine, dimethylethanolamine, hydrazine and phenylhydrazine, and

b. a compound of the formula where n denotes one of the integers l and 2, and R denotes phenyl which may be substituted by halogen or trifluoromethyl or R denotes the radical -N=CH -OH c. a compound of the formula where R denotes methoxy, alkynyl of 5 carbon atoms or a 5-chloro-4-methylthiazolyl radical and X denotes phenoxymethyl bearing halogen and methyl substituents in the phenyl radical, dichlorophenyl, or lower alkyl, or

d. a compound of the formula Q-COOH X where X denotes halogen, methoxy or amino and n de-' notes one of the integers l, 2, 3 and 4, it being possible for methoxy and halogen or amino and halogen or methoxy, amino and halogen to be present simultaneously, or

e. a compound of the formula where Y denotes hydrogen, hydroxy or the radical X denotes halogen and n denotes the integer 2, or

f. a compound of the formula N-cO-O-R where R denotes halophenyl or aminobenzenesulfonyl and R denotes lower alkyl or haloalkynyl of 4 carbon atoms, or

g. 9-hydroxyfluoroenecarboxylic acid-(9), or

h. O,S-dimethyltetrachlorothioterephthalate, or

i. a compound of the formula -CH -CO- and X denotes an anion (Cl', Br, methyl sulfate), or

k. the compound 1,1'-ethylene-2,2-dipyridilium dibromide, have a herbicidal action superior to that of their individual components.

Active ingredients a to k may be applied in amount of 0.5 to 5 kg per hectare.

The weight ratio ofa b, c, d, e,f, g, h, i, or k is from 5:1 to 1:5, preferably from 3:1 to 1:3.

The compositions of the invention are suitable for controlling unwanted plants, e.g. dicotyledonous seed weeds, monocotyledonous grassy seed weeds and Cyperaceae in crops such as cereals, rice, soybeans, Indian corn, potatoes, peas, and beans.

The compositions may be used preand/or postemergence.

The agents according to the invention may be used as solutions, emulsions, suspensions oil dispersions, granules or dusts. The form of application depends entirely on the purpose for which the agents are being used; in any case it should ensure a fine distribution of the active ingredient.

For the preparation of solutions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils and oils of vegetable or mineral origin, and cyclic hydrocarbons such as tetrahydronaphthalene and alkylated naphthalenes are suitable.

Aqueous formulations may be prepared form emulsion concentrates, pastes or wettable powders by adding water. To prepare emulsions the ingredients as such as dissolved in a solvent may be homogenized in water III V 0.75 0.75 kg per hectare;

IV V I 2.0 kg per hectare.

After 8 to 12 days it was ascertained that the compositions had a better overall action than the individual active ingredients, combined with good crop plant compatibility. The results are given below:

Active ingredient I [I III IV V I+V lI+V III+V IV+V kg/hfl 1 2 2 3 0.75 1.5 I 3 0.75 l L5 2 3 l+l 2+1 0.75+0.75 l+2 Trilic'um aesrirum 0 0 IO 20 0 l0 0 0 0 0 0 0 O 0 l0 0 0 Hurdeum i'ulgare 0 0 5 l5 0 l5 0 0 O 0 0 0 l0 0 0 Avvna fuma 7O 9O 50 70 5 5 5 5 1O 85 80 Alopecurus 60 85 50 75 5 5 l0 l0 I5 80 8O myusuraides Galium aparine 5 I0 45 2O 45 30 85 60 70 80 80 90 90 I00 Slellaria media 10 30 4O 65 30 70 30 90 4O 6O 70 90 90 90 I00 I00 I00 Lamium umplexicaule 5 l0 5 I0 80 30 95 30 40 75 I00 I00 0 no damage l00= complete destruction EXAMPLE 2 or organic solvents by means of wetting or dispersing agents, e.g., polyethylene oxide adducts. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent. Oils of various types may be added to ready-to-use spray liquors.

Dusts may be prepared by mixing or grinding the active ingredients with a solid carrier, e.g., clay or fertilizers.

Granules may be prepared by bonding the active ingredients to solid carriers.

Directly sprayable dispersions may also be prepared with oils.

The new compounds may be mixed with fertilizers, insecticides, fungicides and other herbicides.

EXAMPLE 1 The plants wheat (Triticium aestivum), barley (Hordeum vulgare), wild oats (Avena fatua), slender foxtail (Alopecurus myosuroides), catchweed bedstraw (Ga/[um aparine), chickweed (Stellaria media) and henbit (Lamium amplexicaule) were treated at a growth height of 4 to 20 cm with the following amounts of the following individual active ingredients and compositions thereof, each active ingredient and each composition being emulsified or dispersed in 500 liters of water per hectare:

I 4-chlorobutyn-2-yl-1 N-3-chlorophenylcarbamate,

l and 2 kg per hectare; II 5-chloro-4-methyl-2-propionamide thiazole,

2 and 3 kg per hectare; III 3,5-dibromo-4-hydroxybenzaldoxime-0-(2',4'-

dinitrophenyl)- ether, 0.75 and 15 kg per hectare; IV 9-hydroxyfluoroencarboxylic acid-(9),

l and 3 kg per hectare; V 3-isopropyl-2,l,3-benzothiadiazinone- (4)-2,2-

dioxide, 0.75, 1.5, 2 and 3 kg per hectare; I V 1.0 1.0 kg per hectare; II V 2.0 1.0 kg per hectare;

The plants rice (Oryza sativa), soybeans (Soja hispida), Indian corn (Zea mays), wheat (Triticum aestivum), barnyard grass (Echinochloa crus-galli), giant foxtail (Setaria faberii), yellow nutsedge (Cyperus escultentus), common cocklebur (Xanthium pensylvanicum), wild mustard (Sinapis arvensis), waterplam tain (Alisma plantago-aquatica), catchweed bedstraw (Galium aparine), chamomile (Matricaria chamomilla), slender foxtail (Alopecurus myosuroides) and annual bluegrass (Poa annua) were treated at a growth height of4 to 20 cm with the following individual active ingredients and compositions thereof, each active ingredient and each composition being emulsified or dispersed in 500 liters of water per hectare:

I 2,4-dinitro-4-trifluoromethyldiphenyl ether, 1.5 and 3 kg per hectare; II 4'-nitro-2,4,6-trichlorodiphenyl ether,

2 and 3 kg per hectare;

III N-( l,l-dimethylpropynyl)-3,5-

dichlorobenzamide, 1 and 3 kg per hectare;

IV 2-(2-methyl-4-chlorophenoxy)-N- methoxyacetamide, l and 2 kg per hectare; V 2,3,6-trichlorobenzoic acid, 0.5 and 2 kg per hectare; VI 2-methoxy-3,6-dichlorobenzoic acid,

1.5 and 2 kg per hectare; VII 3-isopropyl-2,l ,3-benzthiadiazinone-( 4)-2,2-

dioxide, 0.5, I, 1.5, 2 and 3 kg per hectare;

I+ VII: 1.5 1.5 kg per hectare;

II VII: 2 1 kg per hectare;

III VII: 1 2 kg per hectare;

IV VII: 1 1 kg per hectare;

V VII: 0.5 1.5 kg per hectare;

VI VII: 1.5 0.5 kg per hectare.

After 8 to 14 days it was ascertained that the compositions had a better overall action than the individual active ingredients, combined with good crop plant compatibility. The results are given below:

Active 1 II III IV V VI VII ingredient kg/ha L5 3 2 3 l 3 l 2 0.5 2 1.5 2 0.5 l 1.5 2 3 Oryza saliva I0 25 1O 20 0 O 0 O 0 Soja hispida I0 25 5 25 0 0 0 5 l0 0 2O 0 0 0 0 0 Zea mays Tritium! e 0 2 aexlivum I Echimivll du 1'65 95 60 90 4011: 180) 40 70 .v e LTUS- ulli V, t

I00 complete destruction 0 no damage 100 cumplcte destruction EXA there f: r.

q a l 3-i'sfopropyj-2d,B-hnzothizid In the p the qmwrali l yb ans (tide lisp 1;.) M and Indian corn (Zea mays) and the unwanted plants 45 0.7 and 2 kg per hectare;

barnyard grass (Echinochloa cru s-galli), giant foxtail (Setaria faherii), yellow nutsedge -(Cyperus esculentus), wild IZIIUSFIIZCI (.Sirg a yensisj conrmon cqeklebur X%; 1m;M--* r eds myziirtt r maz q EXAMPLE 4 In the open the crop plants wheat (Triricum aestz'vum), barleyKHordeum vulgafe), ryeKSecgiIe cer eiile) and lawn gra ssTarid the unwanted plants wild mustard (Sinapis arvensis), hempnettle (Galeopsis tetrahit), cat'o'hweed bedstraw (Gdlium aparine), kochia (Kochia scoparia); red deadnettle (Lamium purpureum), gromwell (Lithospermum officinale), chamomile (Matricaria chzinomilla), redroot pigweed (Amarantlzus retroflexus) and common oocklebur (Xanthium pensylvanicum are treated postemergence with the following amounts of the following individual active ingredients and compositions thereof:

I 3,5-dibromo-4-hydroxybenzonitrile, 0.4 kg per hectare; V I II '3,5-diiodo-4-hydroxybenzonitrile, 0.3 kg per hect- ,5 i l," III 3,5-dibromo-4-octanoyloxybenzonitrile, 0.5 kg

per-hectareg IV 3-is'opropyl-2,l ,3-benzothiadiazinone-4)-2,2-

dioxide, 0.5 kg per hectare;

I IV: 0.4 0.5 kg per hectare;

II IV: 0.3 0.5 kg per hectare;

III IV: 0.3 0.5 kg perhectare;

After 10 to 14 days itwas ascertained that'the eom positions had a better herbicidal action than their individual components, combined with the same good ,crop plant compatibility. l

The results are given below:

and a better herbicidal. action than its individual com? ponents.

The results are given below:

0 no damage 7 100 complete destruction EXAMPLE 6 H In the greenhouse the plan'ts and the soil-aregtreated prior, to the emergence of beet (Beta vulgaris) and px tatoes S0lan um 4a berosum) a-nd after the emergence of wheat (Triticum aestivttm) and the unwanted plants; green foxtail (Setaria vifridis), giant foxtail faberii), barnyard grass (Echinochloa crus gz'zl ');sle n derfoxtail (Alopecurus myosuroides), silki/ be g Active ingredient I II III IV I l-IV lI F IV kg/ha 0.4 0.3 0.5 O.4+0.5 0.3%- 0.5

Trilicum aeslivum 5 l0 0 0 Hordeum vulgare 5 0' Secale cer'eale 0 5 0' lawn grass 0 0 0 Sinapis arvensis 30 25 Galeopsis letrahit 25* 3O 25 Galium aparine Y 20 3O """'"'l'5*"'"' 35 Kachia scoparia 25 25 I5 20 133M255 (m Lamium purpureum 3O 40 25 I0 rmitumizub vlolqrrmu \PUl Lilhospermum officinale 25 30 20 25 L Malricaria chamomilla 2O 30 20 -35 4 A ay/". r lrqfl gsur i 5. t 30 Xaniluum pensylvamcum Z0 25 20 I 5 I 90 G am Esq) 3i: m7

0=nodamage l I. 2H. t. 100 complete destruction l e s rowin on t th ut -vvanteq-p nw e ree --.f. ma l. (Seiaria viria'is), yellow foxtail (Setaria glauca),esgiant o i a i f i barnyard-grantEclziuoehlva crus-galli), yellow nutsedge (Cyperuiesculentus), purple nutsedgeACype-rus rotundus), wild mustard Sinapis 55 arverisis-D, chamomile (Mazrica ria chamoinilla), cbm niofi piifs'la'r'ie"""(Pbrfilldifi blfdbelfl, r e droot pigiiieed (Amaranthus retroflexus). and annual bluegrass (Port annua) are treated with the following amourits of thefollowing active ingredients and COmPOSIfiOHyIhGICOfZM I 2,6-diclilbrobenzonitrile, 0.5 kg per hecfitare;

ingredients and compositions thereof:

0.3 ectare;

imethylmorpholinecarbonylmethyl)- 0.5 kgp'er hectare; v if f' o I II: 0.5+ 0.5 kg peri hectarexi i 0 IV '3-lSO'pl 5pyl2,l ,3-benzothiadiazinone-(4)-2,2- 'After IOte l4 days it' was ascertained that the comdio udqfff position had better compatibility with the fruit trees 1 .nm. (hectare;

9 10 I IV: 0.3 0.5 kg per hectare; a. a compound of the formula 11 +1V: 0.5 0.5 kg per hectare; O 111 W: 0.3 0.5 k er hectare.

P After 10 to 14 days it was ascertained that the com- 1 positions had a better herbicidal action than their indiq/ 2 vidual components, combined with the same good crop I plant compatibility. H

The results are given below: where R denotes lower alkyl of a maximum of 4 carbon Active ingredient l II III 1V 1 IV [I 1V 11] lV kg/ha 0.3 0.5 0.3 0.5 0.3 +0.5 0.5 +0.5 0.3 0.5

Bela vulgaris 0 O O O 0 O SOIIIIHUH tuberusum 0 0 O O O 0 0 Triticum aestivum l0 O 5 5 Semria viridis 4O 5 90 8O 85 Selaria faberii 4O 3O 5 95 8O 85 Echinochloa crus-galli 35 25 3O 0 85 75 8O Alopecurus myoxuroides 4O 3O 35 5 8O 7O 75 Apera spica vemi 5O 10 100 90 95 Lolium perenne 35 25 30 O 80 70 Poa lrivialis 4O 3O 35 5 85 8O Galium aparine 35 30 30 35 9O 8O 8O Matricaria chamomilla 4O 35 35 35 95 Sinapis arvensis 45 4O 45 40 100 100 Chemopodium album 45 4O 4O 45 100 100 100 0 no damage 100 complete destruction The action of the following compositions correatoms, or an alkali metal, ammonium, hydroxyalkylamsponds to that of those above: monium, alkylammonium or hydroxy alkylalkyl ammo- 3-isopropyl-2,I,3-benzothiadiazinone-(4)-2,2- nium salt thereof, and

dioxide with methyl-N-(4-aminobenzenesulfonyl)- 30 b. 2,6-dichlorobenzonitrile in a weight ratio ofa to b carbamate, in the range of 5:1 to 1:5. 2-methoxy-3,5,6-trichlorobenzoic acid, 2. A herbicide composition as claimed in claim 1 O,S-dimethyltetrachlorothioterephthalate, or 4'- wherein compound a is 3-isopropyl-2,l ,3-

nitro-2,4-dich1orodiphenyl ether. benzothiadiazinone-(4)-2,2-dioxide. IClaim! 35 3. A herbicide composition as claimed in claim 1 wherein the weight ratio of a to b is 3:1 to 1:3. 1. A herbicidal composltion consisting essentially of 4 A herbicide Composition as Claimed in Claim 2 an inert carrier containing a herbicidally effective wherein the Weight ratio f a to b is 1;1 amount of a mixture of UNITED STATES PATENT OFFICE CETIFICATE 0F CORRECTION PATENT NO. 1 3,888,655 Q DATED June 10, 1975 INVENTOR S I Adolf Fischer it is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In Column 3, Line 3, delete "form" and substitute--from-- In Column 3, Line 6, delete "as" and substitute--or-- In Column 6, Example 3 (Composition I), delete q benzothiacliazinon" and substitute --benzothiadiazinone-- Signed and Scaled this q eighth Day of June 1976 HSEAL] Arrest:

Q RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner ofPatem: and Trademark: 

1. A HERICIDAL COMPOSITION CONSISTING ESSENTIALLY OF AN INERT CARRIER CONTAINING A HERBICIDALLY EFFECTIVE AMOUNT OF A MIXTURE OF A. A COMPOUND OF THE FORMULA
 2. A herbicide composition as claimed in claim 1 wherein compound a is 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide.
 3. A herbicide composition as claimed in claim 1 wherein the weight ratio of a to b is 3:1 to 1:3.
 4. A herbicide composition as claimed in claim 2 wherein the weight ratio of a to b is 1:1. 